Hematite unit cell

The structure derived from a Rietveld fit of a neutron diffraction pattern of a 6-line ferrihydrite which showed more and sharper lines (Fig. 2.9, lower) than an XRD pattern, was in agreement with the structure proposed by Drits et al. (1993) except that it was not necessary to assume the presence of hematite in order to produce a satisfactory fit (Jansen et al. 2002). The unit cell of the defect free phase had a = 0.29514(9) nm and c = 0.9414(9) nm and the average domain size derived from line broadening was 2.7(0.8) nm. Since forced hydrolysis of an Fe solution at elevated temperatures will ultimately lead to hematite, it is likely that incipient hematite formation may occur under certain synthesis conditions. Neither these studies nor Mbssbauer spectroscopy, which showed only a singular isomer shift at 4.2 K characteristic of Fe, supported the presence of " Fe (Cardile, 1988 Pankhurst Pollard, 1992). However, the presence, at the surface, of some Fe with lower (<6) coordination, perhaps as tetrahedra (Eggleton and Fitzpatrick, 1988) which may have become unsaturated on heating, has been suggested on the basis of XAFS results (Zhao et al. 1994). 

Fig. 2.11 Structure of hematite, a) Hexagonal lined, c) Arrangement of octahedra. Note their close packing of oxygens with cations distributed face-sharing, d) Ball-and-stick model. Unit cell in the octahedral interstices. Unit cell outlined. outlined, e) 03-Fe-03-Fe-03 triplets, (a, b Eggle-b) View down the c-axis showing the distribution ton et al., 1988 with permission c, d Stanjek, of Fe ions over a given oxygen layer and the hexa- unpubl. e Stanjek, 1991 with permission) gonal arrangement of octahedra. Unit cell out-...

There are structural analogues of a number of iron oxides in the Fe-H-O system. Under certain conditions, continuous solid solutions exist between the two members of a pair. The magnetite-ulvospinel and the hematite-ilmenite pairs are well-known examples. The principle in going from the Fe oxide to the Ti-containing phase is to replace two Fe by one Fe" and one Ti , thereby increasing the unit cell size. 

A common method of synthesizing M-substituted oxides, particularly goethite and hematite is to add base to mixed M-Fe salt solutions to precipitate M-associated ferrihydrite. Most ions do not change their oxidation state, but incorporation of Mn and Co in goethite is preceded by oxidation of these ions to the trivalent state (Giovanoli Cornell, 1992). An indication of whether isomorphous substitution has occurred can be obtained from changes in the unit cell dimensions of the Fe oxides... 

Fig. 3.9 Effect of Al-substitution in synthetic hematites on (Left) the unit cell edge length a of hematites synthesized at various temperatures (Stanjek Schwertmann, 1992, with permission), and (Right) the magnetic hyperfine field Bhf of hematites formed at 70 °C and 1000°C dotted lines indicate 95% confidence limits (Murad Schwertmann 1986 with permission).

Low levels of structural Ge" have also been observed in natural hematite from the Apex mine, Utah (Bernstein Waychunas, 1987) and to achieve charge balance, incorporation of two Fe for one Ge", i.e. similar to the two Fe" for one in ilme-nite, has been suggested. Synthetic, single crystals of Ge substituted hematite have also been grown by a chemical vapour transport method (Sieber et al. 1985). A range of elements including Zr, Ge, Hf, V, Nb, Ta, W and Pb has been used as low level dopants (2 10 - 0.2 g kg ) to improve the semiconductor behaviour of hematite anodes (Anderman Kermedy, 1988). The increase in unit cell c from 1.3760 to 1.3791 nm and in a from 0.50378 to 0.50433 nm indicated that Nd (as an inactive model for trivalent actinides of similar ionic size (Am r = 0.0983 nm Nd " r = 0.098 nm)) was incorporated in the structure (Nagano et al. 1999). 

Galvez et al. (1999) demonstrated that phosphorus up to a P/Fe mol ratio of 0.03 mol mol , can be incorporated into the hematite structure by heating P-con-taining 2-line ferrihydrite. Support for structural incorporation comes from a higher unit cell c (1.3776 => 1.3824 nm), IR-stretching bands of P-OH, a lowered intensity ratio of the XRD 104/113 lines and congruent release of Fe and P upon dissolution. 

Extensive replacement of Fe by transition metal cations and alkaline earth ions has been reported for b-FeOOH (Okamoto, 1968). Muller et al. (1979) found incorporation of up to 0.4 mol moF Ca solid solutions with the formula Fei xKxOi x(OH)i+x could be identified. Jimenez-Mateos et al. (1990) reported that Co and Mn, respectively, could replace up to 0.3 and 0.5 mol mol Fe. The unit cell parameters decreased in both cases with increasing substitution. These Mn- and Co-substituted 5-FeOOHs decomposed at 200 °C to give poorly crystalline, substituted hematites. 

The thermal transformation of feroxyhyte (5 -FeOOH) was studied by Carlson and Schwertmann (1980). Synthetic feroxyhyte transformed to hematite with non-uni-formly broadened XRD lines at 240 °C (DTA). As the temperature increased further, an exothermic peak appeared and the crystallinity of the hematite improved. In an atmosphere of N2 the transformation of natural feroxyhyte was impeded. As the temperature rose, the crystallinity of this feroxyhyte improved and at 460 °C, the a unit cell edge length dropped from 0.5062 to 0.5027 nm. As this sample contained organic impurities, the final transformation product in this case, even at 800 °C, was maghemite (see p. 368). 

Fig. 4.1 The crystal structure of hematite as seen looking down the [001] direction (left) and the [8] direction (right). Oxygen anions are dark gray and iron cations are light gray. The unit cell is outlined, and the orientation map is shown for each view...

Figure 42. Illustration of two possible (001) terminations of hematite. Along [001], the bulk repeat unit is 18 atomic planes thick ( 13.7 A conventional cell). An electrostatically stable (non-polar) termination (labeled Fe-Os-Fe) is found by dividing the stmcture between Fe-Fe planes in a bilayer (a). This leaves a 1/3 monolayer of Fe over a close packed oxygen layer. A polar oxygen terminated surface is created by dividing the structure just above oxygen planes (labeled Os-Fe-Fe). Both have been experimentally and theoretically identified (see text). The uppermost planes of the Fe-Os-Fe termination (to a depth of two atomic planes below the uppermost O plane) consist of three Fe sites labeled A, B, and C (b). Using the same labeling scheme, the uppermost planes of the Os-Fe-Fe termination are shown in (c). The hexagonal unit cell is outlined ( 5 A).

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